US4524224A - Hydrolysis of alkylene carbonates to aklylene glycols - Google Patents

Hydrolysis of alkylene carbonates to aklylene glycols Download PDF

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Publication number
US4524224A
US4524224A US06/495,462 US49546283A US4524224A US 4524224 A US4524224 A US 4524224A US 49546283 A US49546283 A US 49546283A US 4524224 A US4524224 A US 4524224A
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carbonate
alkylene
glycol
water
reaction
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US06/495,462
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English (en)
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Glenn A. Taylor
Philip F. Wolf
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • This invention is concerned with the production of an alkylene glycol by the hydrolysis of the corresponding alkylene carbonate. More particular, this invention relates to a process which achieves better rates of reaction and exceptional efficiency of conversion by hydrolysis of alkylene carbonates to the glycols.
  • the process of this invention can be utilized to produce ethylene glycol which when catalyst and water are removed can meet the stringent requirements of Polyester Fiber grade, see companion patent application Ser. No. 863,354, filed Dec. 22, 1977, now U.S. Pat. No. 4,314,945, for a definition thereof.
  • potassium carbonate was not a catalyst of choice but used only as a buffer, producing a mild alkaline solution, to study the mechanisms of alkaline induced ester hydrolysis, in dilute solutions.
  • the catalyst employed in the process of this invention may be any potassium compound which when incorporated into protic medium under carbon dioxide pressure produces potassium carbonate, either as the ionic form or potassium bicarbonate form.
  • the amount of the catalyst that one employs in practicing the process of this invention contributes significantly to the rate of the reaction.
  • the amount of the catalyst based on the weight of alkylene carbonate, can be as little as 0.03 weight percent to as much as 10 weight percent. In making these calculations the catalyst is considered to be potassium carbonate.
  • the preferred amount of catalyst is about 0.1 to about 5.0 weight percent. To achieve the greatest catalytic effect for the amount of catalyst employed, the most preferred amount of the catalyst is 0.25 weight percent to about 1.5 weight percent, based on the weight of alkylene carbonate.
  • the minimum temperature to employ is 85° C.
  • the temperature may be as high as 500° C. and when temperatures that high are employed it is desirable to make adjustments in the amount of catalyst employed; the smaller amount of catalyst compensating for the increased temperature.
  • the preferred temperature is between about 120° and 200° C.
  • the reaction is also carried out under pressure utilizing a carbon dioxide pressure of greater than 80 psig.
  • a carbon dioxide pressure of greater than 80 psig.
  • there are practical considerations which one can employ in determining a maximum pressure In terms of economic benefits it would be desirable not to employ a pressure exceeding 2000 psig. Most desirably the maximum pressure does not exceed about 1000 psig.
  • pressure one has to take into consideration the type of equipment which is available and being utilized. Should this process be carried out in available equipment which is capable of taking very high pressure and there appears to be under any conditions of the reaction sufficient reason for doing so because of the fact that higher pressure carbon dioxide is available, then of course the disadvantages that would be attributable to the use of such higher pressures will be mitigated.
  • Another factor to be considered in carrying out the process of this invention is the amount of water which is provided in the feed to the reactor in which the reaction is either effected, in a batch or continuous operation.
  • the initial mole ratio of water to alkylene carbonate which is employed in the hydrolysis reaction should be at least one mole of water per mole of alkylene carbonate.
  • the most preferred ratio is about 1.5 to 2.5:1.
  • mole ratios below 1.2 make it difficult to minimize the production of diethylene glycol or dispropylene glycol.
  • the process of this invention can be operated in the presence of a solvent which serves the purpose of, at the most, diluting the reaction mixture.
  • a solvent which serves the purpose of, at the most, diluting the reaction mixture.
  • Any liquid at the reaction temperature which is miscible with the alkylene carbonate and the glycol product can be, to the extent that it continues to be miscible in the system, a solvent provided that it is not reactive with either the alkylene carbonate reactant, the glycol produced or the potassium catalyst employed.
  • Such chemicals as carboxylic acids, phenols, aldehydes, alkylene oxides, other than ethers of the non-vicinyl type, may not be employed as solvents in the practice of this invention.
  • Alkylene carbonates and the resulting alkylene glycol are very good solvents.
  • the alkylene carbonate employed is the same as the alkylene carbonate reactant and that the glycol employed as a solvent is the same as the product glycol being produced.
  • the only effect that one obtains from the use of such solvents is that they reduce, to the extent of dilution, the rate of reaction. However, they do not adversely affect the percent conversion or the efficiency of the reaction. They are useful for the purpose of controlling reaction temperature and rate; and assist in recycle systems when this is carried out in a continuous fashion.
  • the process of this invention may be carried out as a batch reaction or as a continuous process.
  • the batch reactions may be carried out in pressure resistant vessels suitably constructed to withstand the pressures of this reaction.
  • the process may be employed in a conventional autoclave or can be effected in a glassware type of equipment when operated at moderate pressures. It may also be employed in a plug-flow reactor utilizing conventional procedures to effect the process continuously. Solvent may be recycled and catalyst may be recovered. The process is very advantageously employed by concentrating the catalyst over a vacuum evaporator and recycling it to the reaction.
  • reaction may be carried out for very short periods of time in terms of fractions of a second and if desired may be carried out over reaction periods amounting to hours. These conditions of reaction are governed by the amounts of solvent and catalyst employed, the pressures and temperatures employed, and like considerations. A most favorable utilization of this invention may be found in copending application Ser. No. 863,352, filed Dec. 22, 1977, now U.S. Pat. No. 4,117,250.
  • the contents of the autoclave were mixed with a dispersimax-type agitator 5 inches in diameter comprised of 6 flat blades.
  • the autoclave was supplied with an internal steam coil and external electric heaters. Cooling was accomplished by adding water to the internal coil through a series of valves.
  • the reactor was charged with a mixture of ethylene carbonate (4000 grams, 45.45 moles), water (1536 grams, 90.0 moles) and monoethylene glycol (285 grams, 4.6 moles) and heated by use of 200 psig of steam in the internal reactor coils and external electrical heaters.
  • ethylene carbonate 4000 grams, 45.45 moles
  • water 1536 grams, 90.0 moles
  • monoethylene glycol 285 grams, 4.6 moles
  • the catalyst 48 grams of 0.35 moles, K 2 CO 3 dissolved in 100 grams of water was charged to the reactor.
  • the feed mole ratio of water to ethylene glycol was 2.0; the feed of K 2 CO 3 concentration (weight percent based on ethylene carbonate feed) was 1.2; the feed monoethylene glycol (weight percent based on total feed) was 5.0.
  • the mixture was agitated at 1000 rpm. Temperature was controlled via a single thermocouple centered in the liquid phase and pressure control was achieved by a backpressure regulator on the discharge line. A vapor phase, consisting principally of CO 2 and water was continuously discharged during reaction. A record of the time elapsed during the discharge of each 0.25 cubic foot of vapor was made by linking a strip chart recorder to a photocell which in turn monitored a dry test meter equipped with a metal cross on the indicator dial. This cross interrupted the light to the photocell every quarter revolution of the meter dial. Off-gas rate was corrected to standard conditions by use of continuous temperature and pressure measurements at the outlet of the gas meter.
  • the reactor contents were discharged and weighed to determine efficiencies. Rates of reaction were based on the total amount of off-gas accumulated as a function of time. The time to reach percent conversion at 150° C., 500 psig, 2.0 feed mole ratio of water to ethylene carbonate, 1.2 weight percent of K 2 CO 3 and 5.0 weight percent of monoethylene glycol was 1.3, 4.0, 6.5, 11.6, and 14.4 minutes respectively at 20, 50, 70, 90 and 95 percent conversion, respectively, of ethylene carbonate to monoethylene glycol.
  • Example 1 was exactly repeated except that reaction temperature and pressure; feed mole ratio of water to ethylene glycol (A); feed K 2 CO 3 concentration, weight percent based on ethylene glycol feed (B); feed monoethylene glycol concentration, weight percent based on total feed (C); and the time in minutes to reach the percent conversion (20, 50, 70, 90 and 95) at the aforesaid conditions (based on CO 2 evolution) are as set forth in TABLE I.
  • a 120 cc Parr bomb equipped with a sample line, thermocouple and a magnetic stirring bar was assembled. CO 2 evolution was monitored with a wet test meter modified by adding five metallic contact points to the face of the meter and connecting them to a telemeter switch, to produce a line on a variable speed recorder every 0.5 liters.
  • the Parr bomb was heated with an electric heater and pressure was regulated using a Nupre adjustable in-line relief valve.
  • the Parr bomb was charged with ethylene carbonate (88.0 grams, 1.0 mole), water (36.0 grams, 2.0 moles) and K 2 CO 3 catalyst (0.5 gram, 0.57 weight percent based on ethylene carbonate).
  • the system was pressurized with CO 2 until 3.0 liters had passed through the wet test meter. At this point, the flow was turned off and the mixture allowed to stand until no further CO 2 absorption was observed.
  • the system as brought to a temperature of 130° C. and a pressure of 108 psig and stirring was begun. A vapor phase consisting principally of CO 2 and water was continuously discharged during the reaction.
  • a record of the time elapsed during discharge of each 0.5 liter of vapor was made by linking a recorder to the above mentioned modified telometer switch which in turn monitored a wet test meter.
  • the reaction contents were discharged and weighed to determine efficiencies. Rates of reaction were based on the total amount of off-gas accumulated as a function of time.
  • the feed mole ratio of water to ethylene carbonate was 2.0; the feed of K 2 CO 3 concentration (weight percent based on ethylene carbonate feed) was 0.60.
  • the time to reach percent conversion at 130° C., 108 psig, 2.0 feed mole ratio of water to ethylene carbonate, 0.6 weight percent of K 2 CO 3 was 11.9, 31.8, 54.0, 92.0 and 105 minutes at 20, 50, 70, 90, 95 percent conversions of ethylene carbonate to monoethylene glycol, respectively.
  • Example 17 was exactly repeated except that reaction temperature and pressure; feed mole ratio of water to ethylene carbonate (A); feed K 2 CO 3 concentration, weight percent was based on ethylene carbonate feed (B); and the time in minutes to reach the percent conversion (20, 50, 70, 90, and 95) at the aforesaid conditions (based on CO 2 evolution) are set forth in TABLE II.
  • Example 17 was exactly repeated except that monoethylene glycol was charged with the ethylene carbonate, water and K 2 CO 3 catalyst.
  • the reaction temperature and pressure; feed mole ratio of water to ethylene carbonate (A); feed K 2 CO 3 concentration, weight percent based on ethylene carbonate feed (B); monoethylene glycol concentration, weight percent based on total feed (C); and the time in minutes to reach the percent conversion (20, 50, 70, 90, and 95) at the aforesaid conditions (based on CO 2 evolution) are set forth in TABLE II.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US06/495,462 1977-12-22 1983-05-20 Hydrolysis of alkylene carbonates to aklylene glycols Expired - Lifetime US4524224A (en)

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US86335177A 1977-12-22 1977-12-22

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US (1) US4524224A (enrdf_load_stackoverflow)
JP (1) JPS5490106A (enrdf_load_stackoverflow)
BE (1) BE872957A (enrdf_load_stackoverflow)
CA (1) CA1107301A (enrdf_load_stackoverflow)
DE (1) DE2855233C3 (enrdf_load_stackoverflow)
FR (1) FR2412515A1 (enrdf_load_stackoverflow)
GB (1) GB2011401B (enrdf_load_stackoverflow)
IT (1) IT1102416B (enrdf_load_stackoverflow)
NL (1) NL7812444A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5969056A (en) * 1999-01-14 1999-10-19 Reichhold, Inc. Process for preparing esterification products from cyclic organic carbonates using catalysts comprising quaternary ammonium salts
US5998568A (en) * 1999-01-14 1999-12-07 Reichhold, Inc. Polyesters prepared from alkoxylated intermediates
US20040267059A1 (en) * 2003-06-06 2004-12-30 Powell Joseph Broun Process for the production of alkylene glycols using homogeneous catalysts
CN114057564A (zh) * 2021-12-09 2022-02-18 上海卓笙环保科技有限公司 一种基于碳酸体系作为无痕催化剂水解乙醇酸酯的方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4117250A (en) * 1977-12-22 1978-09-26 Union Carbide Corporation Continuous process for producing alkylene glycols from alkylene carbonates
DE2931753C2 (de) * 1979-08-04 1984-10-04 Akzo Gmbh, 5600 Wuppertal Verfahren zur Herstellung von vicinalen Alkylenglykolen
DE3147737A1 (de) * 1981-12-02 1983-06-09 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von cyclischen 1,2-cis-diolen aus cyclischen 1,2-epoxiden

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU267618A1 (ru) * Способ получения алкиленгликолей
US3629343A (en) * 1968-10-11 1971-12-21 Vnii Neftekhim Protsessov Process for the production of alkylene glycols
US4117250A (en) * 1977-12-22 1978-09-26 Union Carbide Corporation Continuous process for producing alkylene glycols from alkylene carbonates

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6808047A (enrdf_load_stackoverflow) * 1968-06-07 1969-12-09 Koninklijke Gist Spiritus
DE1793247C3 (de) * 1968-08-21 1973-11-29 Wsesojusnij Nautschno-Issledowatel' Skij Institut Neftechimitscheskich Prozessow, Leningrad (Sowjetunion) Verfahren zur Herstellung von Alkylenglykolen
GB1177877A (en) * 1968-08-26 1970-01-14 Vnii Neftekhim Protsessov Process for the Production of Alkylene Glycols

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU267618A1 (ru) * Способ получения алкиленгликолей
US3629343A (en) * 1968-10-11 1971-12-21 Vnii Neftekhim Protsessov Process for the production of alkylene glycols
US4117250A (en) * 1977-12-22 1978-09-26 Union Carbide Corporation Continuous process for producing alkylene glycols from alkylene carbonates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5969056A (en) * 1999-01-14 1999-10-19 Reichhold, Inc. Process for preparing esterification products from cyclic organic carbonates using catalysts comprising quaternary ammonium salts
US5998568A (en) * 1999-01-14 1999-12-07 Reichhold, Inc. Polyesters prepared from alkoxylated intermediates
US20040267059A1 (en) * 2003-06-06 2004-12-30 Powell Joseph Broun Process for the production of alkylene glycols using homogeneous catalysts
US7683221B2 (en) 2003-06-06 2010-03-23 Shell Oil Company Process for the production of alkylene glycols using homogeneous catalysts
CN114057564A (zh) * 2021-12-09 2022-02-18 上海卓笙环保科技有限公司 一种基于碳酸体系作为无痕催化剂水解乙醇酸酯的方法
CN114057564B (zh) * 2021-12-09 2023-10-03 上海卓笙环保科技有限公司 一种基于碳酸体系作为无痕催化剂水解乙醇酸酯的方法

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GB2011401B (en) 1982-05-19
GB2011401A (en) 1979-07-11
FR2412515B1 (enrdf_load_stackoverflow) 1984-06-29
NL7812444A (nl) 1979-06-26
BE872957A (fr) 1979-06-21
IT1102416B (it) 1985-10-07
DE2855233B2 (de) 1981-01-22
JPH0156056B2 (enrdf_load_stackoverflow) 1989-11-28
JPS5490106A (en) 1979-07-17
FR2412515A1 (fr) 1979-07-20
IT7831176A0 (it) 1978-12-21
DE2855233C3 (de) 1987-07-30
DE2855233A1 (de) 1979-06-28
CA1107301A (en) 1981-08-18

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